Mass spectrometers purpose

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

Gas chromatography also can be used for qualitative purposes. When using an FT-IR or a mass spectrometer as the detector, the available spectral information often can be used to identify individual solutes. 

The previous discussion has concentrated on major factors likely to be important in choosing the best mass spectrometer for a given defined purpose. Clearly, there are likely to be other issues that need to be considered, and instrument price will be one of these. The major considerations are listed in Tables 39.1-4. 

The three isotopes of hydrogen are almost indistinguishable for most chemical purposes, but a mass Spectrometer can see them as three different entities of mass 1, 2, and 3 Da. Isotopes of other elements can also be distinguished. Mass spectrometry is important for its ability to separate the isotopes of elements. 

Multidimensional or hyphenated instmments employ two or more analytical instmmental techniques, either sequentially, or in parallel. Hence, one can have multidimensional separations, eg, hplc/gc, identifications, ms/ms, or separations/identifications, such as gc/ms (see CHROMATOGRAPHY Mass spectrometry). The purpose of interfacing two or more analytical instmments is to increase the analytical information while reducing data acquisition time. For example, in tandem-mass spectrometry (ms/ms) (17,18), the first mass spectrometer appHes soft ionization to separate the mixture of choice into molecular ions the second mass spectrometer obtains the mass spectmm of each ion. 

In earlier procedures, the ReO anion was precipitated from water as the relatively insoluble potassium salt. Reduction of KReO with hydrogen gas gives rhenium metal, but the metal is contaminated with ca 0.4 wt % potassium that cannot be separated easily. Although suitable for some purposes, rhenium formed from KReO is found to be unsatisfactory in appHcations such as those for use in filaments in mass spectrometer systems. The route involving NH ReO avoids this problem. 

In the process of SNMS analysis, sputtered atoms are ionized while passii through the ionizer and are accelerated into the mass spectrometer for mass analysis. The ion currents of the analyzed ions are measured and recorded as a function of mass while stepping the mass spectrometer through the desired mass or element sequence. If the purpose of the analysis is to develop a depth profile to characterize the surface and subsurface regions of the sample, the selected sequence is repeated a number of times to record the variation in ion current of a selected elemental isotope as the sample surfiice is sputtered away. 

Demonstration of GDMS feasibility and research into glow-discharge processes has been carried out almost exclusively using the combination of a glow-discharge ion source with a quadrupole mass spectrometer (GDQMS). The combination is inexpensive, readily available and suitable for such purposes. In addition, the quadru-... 

Analytical information taken from a chromatogram has almost exclusively involved either retention data (retention times, capacity factors, etc.) for peak identification or peak heights and peak areas for quantitative assessment. The width of the peak has been rarely used for analytical purposes, except occasionally to obtain approximate values for peak areas. Nevertheless, as seen from the Rate Theory, the peak width is inversely proportional to the solute diffusivity which, in turn, is a function of the solute molecular weight. It follows that for high molecular weight materials, particularly those that cannot be volatalized in the ionization source of a mass spectrometer, peak width measurement offers an approximate source of molecular weight data for very intractable solutes. 

These authors also analysed marine diesel fuel with GC X GC, connected to a quadrupole mass spectrometer for identification purposes, although the scan speed of the spectrometer was not quite suited for the fast second-dimension peaks... 

Tandem quadrupole and magnetic-sector mass spectrometers as well as FT-ICR and ion trap instruments have been employed in MS/MS experiments involving precursor/product/neutral relationships. Fragmentation can be the result of a metastable decomposition or collision-induced dissociation (CID). The purpose of this type of instrumentation is to identify, qualitatively or quantitatively, specific compounds contained in complex mixtures. This method provides high sensitivity and high specificity. The instrumentation commonly applied in GC/MS is discussed under the MS/MS Instrumentation heading, which appears earlier in this chapter. 

When a pulsed laser is used, ions are only produced for the duration of the pulse, i.e. they are not produced continuously and the mass spectrometer used must be capable of producing a mass spectrum from these pulses of ions. As discussed below in Section 3.3.4, the time-of-flight (ToF) mass analyser is the most appropriate for this purpose and has the added advantage of being able to measure very high m/z ratios. Indeed, the recent dramatic developments in the performance of the ToF mass analyser have largely been occasioned by the requirement to produce useful spectra from MALDI. 

For this purpose we studied a temperature-programmed interaction of CH with a-oxygen. Experiments were carried out in a static setup with FeZSM-5 zeolite catalyst containing 0.80 wt % Fe203. The setup was equipped with an on-line mass-spectrometer and a microreactor which can be easily isolated from the rest part of the reaction volume. The sample pretreatment procedure was as follows. After heating in dioxygen at 823 K FeZSM-5 cooled down to 523 K. At this temperature, N2O decomposition was performed at 108 Pa to provide the a-oxygen deposition on the surface. After evacuation, the reactor was cooled down to the room temperature, and CH4 was fed into the reaction volume at 108 Pa. 

Analytical standards are prepared for two purposes for fortifying control matrices to determine the analytical accuracy and for calibrating the response of the analyte in the mass spectrometer detector. The purity of all standards must be verified before preparation of the stock solutions. All standards should be refrigerated (2-10 °C) in clean amber-glass bottles with foil/Tefion-lined screw-caps. The absolute volume of the standard solutions may be varied at the discretion of the analyst, as long as the correct proportions of the solute and solvent are maintained. Calibrate the analytical balance before weighing any analytical standard material for this method. 

GC/MS. GC/MS is used for separation and quantification of the herbicides. Data acquisition is effected with a data system that provides complete instrument control of the mass spectrometer. The instrument is tuned and mass calibrated in the El mode. Typically, four ions are monitored for each analyte (two ions for each herbicide and two ions for the deuterated analog). If there are interferences with the quantification ion, the confirmation ion may be used for quantification purposes. The typical quantification and confirmation ions for the analytes are shown in Table 4. Alternative ions may be used if they provide better data. 

Such techniques imply analysis of chemical products of photolysis. Application of mass-spectrometers of various types is often hampered by a number of circumstances. These difficulties will be discussed later on. The EPR method, which is currently the most extensively employed technique, features low sensitivity and is usually used for analysis of primary fragments of photolysis. For this purpose, the radicals produced are frozen on the walls of a quartz pin and are thus accumulated inside the device. On one hand, this approach allows one to overcome the sensitivity threshold of the device. However, on the other hand, this excludes the possibility of direct kinetic measurements. The SS technique permits the use of weak light sources for detecting active particles under... 

Apparatus, developed in this laboratory for two types of thermochemical measurements—(a) gas-phase ion molecule equilibria and (b) collision-induced dissociation (CID) threshold measurements—will be described. For both purposes, a triple quadrupole mass spectrometer is used. It is only the front end modifications that provide the conditions for (a) or (b). 

A mass spectrometer is often indispensable for a complete analysis of low-pressure gases, but a description of the various types of spectrometers is beyond the purpose of this book, but see, for example, ref. [18]. We simply remind that a mass spectrometer consists of three parts an ion source where the neutral gas is ionized (usually by electron bombardment) an analyser where ions are selected according to their mass to charge ratio and a collector with an amplifier to measure the weak ion current. 

A cryogenist does not usually need a general purpose mass spectrometer, but the cryogenist cannot work without an LD which is made up of a small vacuum system (rotary pump or diaphragm pump in series with a turbo pump) and a mass spectrometer for the detection of light gases (H2,3He and 4He). 

The earlier stable isotope dilution mass spectrographic work was accomplished with a thermal ion mass spectrometer which had been specifically designed for isotope abundance measurements. However, Leipziger [829] demonstrated that the spark source mass spectrometer could also be used satisfactorily for this purpose. Although it did not possess the excellent precision of the thermal unit, Paulsen and coworkers [830] pointed out that it did have a number of important advantages. 

Once into the 21st century, hyphenated instrumentation (i.e., those that couple two instruments together) became prevalent in laboratories. This is the combination of two or more, often different, instruments. In simple terms, the purpose is to first separate the analyte of interest and then to identify it. This takes place using a sample injected into the combined instruments. The most common of the hyphenated instruments is the gas chromatograph, the output of which is fed into a mass spectrometer to produce a gas chromatography-mass spectrometry (GC-MS) [35],... 

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